Refractory casting method

ABSTRACT

A method of casting a refractory article. The method includes providing a mold formed from a slurry composition comprising plaster and fibers and adding a refractory composition to the mold. The method also includes allowing the refractory composition to set. The refractory composition comprises colloidal silica.

FIELD OF INVENTION

This invention relates to the production of thin-film piezoelectric materials. More particularly this invention relates to a sol-gel process for producing thin films of ferroelectric or piezoelectric materials such as Pb(Zr,Ti)O₃, known as PZT, or lanthanum doped PZT, known as PLZT, or PZT doped with elements such as niobium and the product thereof. It also relates to a sol gel process for producing crack free thin films of other complex oxides such as zirconia, calcium apatite, and barium titanate, among others.

BACKGROUND OF INVENTION

The ferroelectric effect is the property of certain crystalline dielectric materials to retain polarization following their polarization. The piezoelectric effect is the property of certain crystalline dielectric materials, when polarized, to generate an electric field or potential of one polarity when a compressive force is applied and the reverse polarity when a tensile force is applied. Conversely, a piezoelectric material will tend to compress if an electric field of one polarity is applied and to expand if an electric field of the opposite polarity is applied.

Thin film materials which are transparent and show good optically non linear properties are in great demand for integrated optics among other uses for such thin film materials. Undoped PZT is an opaque ferroelectric ceramic and therefore its nonlinear optical effects, if any, cannot be measured. However, the addition of lanthanum to form La-doped PZT, or PLZT, causes the material to become transparent and to show large electro-optic effects. In addition to electro-optic properties, PZT has a large pyro-electric response, large electromechanical coupling coefficient high dielectric constant and a large spontaneous polarization, all of which are useful properties for incorporation into infra red detectors, surface acoustic wave devices, ferroelectric nonvolatile semiconductor memories, and devices requiring transtarent high permittivity layers such as electroluminescent displays.

Several methods for producing PZT, or PLZT (lanthanum doped) thin films have been developed over the past decade, primarily using techniques such as flash and electron beam evaporation, rf sputtering, ion beam deposition and epitaxial growth by rf sputtering. However such techniques are generally difficult to control, are relatively time consuming and require expensive apparatus. Chemical sol gel processing of PZT of PLZT thin films has also been suggested. Sol gel processing offers significant advantages over vacuum deposition techniques such as easier composition control and film homogeneity, easier fabrication of large area thin films, low cost and short processing cycles. However, sol gel processing is not without its difficulties, particularly with respect to fabricating relatively thick crack free PZT thin films. The thickness of PZT or PLZT thin film strongly influences film properties such as dielectric constant, remanent polarization and coercive field.

While the present invention will be described with particular reference to the production of PZT and PLZT thin films, the sol-gel processing method is equally applicable to other complex oxide thin films. As used herein the term “complex oxide” includes:

-   -   Alumina     -   Zirconia     -   Calcium titanate     -   Calcium apatite     -   Lithium niobate     -   Barium titanate     -   Tantalum zirconate     -   Magnesium tantalate     -   Yttrium Barium Copper Oxides     -   Yttrium Oxide     -   Barium Calcium Thalium Copper Oxide

OBJECT OF INVENTION

It is, therefore, an object of the present invention to overcome the deficiencies of the prior art and provide an improved sol gel processing method for making thin film piezoelectric materials which are substantially crack free, and which have improved physical properties.

Another object of the invention is to provide PZT thin films having a piezoelectric coupling coefficient of at least 1%.

It is yet another object of the invention to provide crack free complex oxide thin films by an improved sol gel process.

STATEMENT OF INVENTION

By one aspect of this invention there is provided a method for preparing a composite of a substrate having deposited thereon a crack-free ferroelectric polycrystalline lead zirconate titanate thin film, comprising

-   -   (a) dissolving lead acetate in acetic acid, adding thereto         zirconium propoxide followed by titanium isopropoxide in         relative proportions to produce a selected ratio of metals, and         agitating until all solids are in solution;     -   (b) adding a firing agent selected from glycerol, ethylene         glycol, tetra ethylene glycol, polyethylene glycol and mixtures         thereof, to said solution;     -   (c) adjusting viscosity of said solution;     -   (d) coating said substrate with said solution so as to form a         wet film thereon;     -   (e) firing said coated substrate at a temperature in the range         300° C.-550° C. so as to pyrolyse said film;     -   (f) annealing said pyrolysed film at a temperature up to about         600° C. for sufficient time to produce a perovskite structure in         said film; and     -   (g) electrically poling said film so as to produce piezoelectric         properties therein.

By another aspect of this invention there is provided a method for preparing a composite of a substrate having deposited thereon a crack free ferroelectric polycrystalline lead zirconate titanate thin film, comprising:

-   -   (a) depositing an oxide film on said substrate;     -   (b) dissolving lead acetate in acetic acid, adding thereto         zirconium propoxide followed by titanium isopropoxide in         relative proportions to produce a selected ratio of metals, and         agitating until all solids are in solution;     -   (c) adding a firing agent selected from glycerol, ethylene         glycol, tetra ethylene glycol, polyethylene glycol and mixtures         thereof to said solution;     -   (d) adjusting viscosity of said solution;     -   (e) coating said oxide coated substrate with said solution so as         to form a wet film thereon;     -   (f) firing said coated substrate at a temperature in the range         300° C.-550° C. so as to pyrolize said film.     -   (g) annealing said pyrolysed film at a temperature up to about         600° C. for sufficient time to produce a perovskite structure in         said film; and     -   (h) electrically poling said film so as to produce piezoelectric         properties therein.

By yet another aspect of this invention there is provided a composite comprising a substrate having deposited thereon a substantially crack-free ferroelectric poly-crystalline lead zirconate titanate thin film having a piezoelectric coupling coefficient of at least 1%. By a further aspect of this invention there is provided a method for preparing a composite comprising a substrate having deposited thereon a crack free complex oxide thin film, comprising:

-   -   (a) preparing a solution containing precursors for said complex         oxides;     -   (b) adding to said solution a firing agent selected from         glycerol, ethylene glycol, tetra ethylene glycol, polyethylene         glycol and mixtures thereof in relative proportions and amounts         so as to provide a solution having a selected viscosity;     -   (c) coating said substrate with said solution so as to form a         wet film thereon; and     -   (d) firing said coated substrate at a temperature in the range         300° C.-550° C. so as to pyrolyse said film.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a block flow diagram illustrating sol gel processing of PZT films.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Sol gel processing has been described previously (see, for example, Sol-Gel Processing of PbTiO₃, PbZrO₃, PZT and PLZT Thin Films, Budd et al Brit. Cer. Proc. 36 (1985) pp 107-121) and depends upon the fact that the components of a complex solution can remain mixed during firing if a gel, a form of polymerised liquid, can be formed. The standard procedure normally includes the steps of (a) forming a stock solution (b) coating the solution onto a substrate either by spin or dip coating (c) firing the wet film or coating to an inorganic form, (d) annealing at high temperature to obtain the required structure and (e) polarizing the film to induce piezoelectric activity. It has now been discovered that the basic process can be improved in ways which are vital to industrial application and which permit the use of a wide range of compositions. Specifically a new stable precursor solution using a chelating agent has been developed and an additive which controls and improves the firing cycle for film fabrication and which improves the surface smoothness of the final film and substantially eliminates macro cracking of the final surface has also been developed. FIG. 1 illustrates a preferred process for making the improved PZT and PZLT films of the present invention. The choice of the precursor compounds and the solvents therefor is important to success. The compounds should have high metal content and high solubility in the selected solvent. They should thermally decompose without evaporating and be chemically compatible with each other. Preferred compounds having the aforesaid properties include: Lead acetate, Zirconium propoxide and Titanium propoxide. The solvent must have an appropriate boiling point and suitable viscosity and surface tension properties. Preferred solvents include water and propanol. The chelating agent, which is required to prevent hydrolysis of the properties is preferably glacial acetic acid although other acids can be used. In order to substantially eliminate macroscopic cracking and to improve the surface smoothness of the film, a firing additive selected from glycerol, ethylene glycol, tetra ethylene glycol, polyethylene glycol and mixtures thereof is preferably incorporated.

Preparation of Solutions for PZT Films

Lead acetate is dissolved in heated acetic acid in the proportion of 2 g lead acetate to 1 ml acetic acid and heated to 105° C. to remove water. The dehydrated solution should be cooled below 80° C. before sequentially adding the required quantities of zirconium propoxide and titanium isopropoxide. It is essential that the zirconium propoxide is added first because it reacts with the acetic acid to form a non-hydrolysable solution which in turn protects the titanium isopropoxide from hydrolysis and condensation when it is added. Conversely, if titanium isopropoxide is added first it reacts with the acetic acid to form mono or diacetylates and condensation occurs with the formation of polytitanyl acetylates. The zirconium-titanium bearing mixture is agitated, preferably in an ultra sonic cleaning tank, until all of the solids present have dissolved. The firing additive which controls the viscosity and the decomposition temperature, is selected from glycerol, ethylene glycol, tetra ethylene glycol, polyethylene glycol or mixtures thereof, and can then be added to the stock solution. Ethylene glycol or glycerol is preferably added in the proportion of 1 ml to 10 g of lead acetate in the solution depending on the thickness of film required. The viscosity and surface tension of the solution can then be adjusted by adding water, propanol or mixtures thereof. Thinner films result from lower viscosity solutions and propanol reduces surface tension thereby improving wettability of the substrate.

Particularly suitable solutions for preparing single layer films 1 m thick of (a) PZT having a composition near the morphotropic phase boundary (Zr/Ti=53.5/46.5) and (b) alumina are shown below in Table 1. TABLE 1 Film Chemical Quantity (a) PZT Lead Acetate Pb(CH₃CO₂)₂3H₂O 12.00 g Acetic Acid CH₃COOH 6 ml Zirconium propoxide Zr(C₃H₂O)₄ 5.54 g Titanium isopropoxide Ti[(CH₃)₂CHO]₄ 2.18 g Ethylene Glycol OHCH₂CH₂OH 1.2 ml Distilled Water H₂O 6 ml (b) Al₂O₃ Aluminum isopropoxide Al[(CH₃)₂CHO]₃ 4 g Nitric Acid HNO₃ 5 ml Ethylene Glycol OHCH₂CH₂OH 4 ml Propanol CH₃CH₂CH₂OH 4 ml

The final solution, which is stable in air, may be filtered through a membrane filter (pore size 0.22 μm) and stored in a sealed container.

Substrate Surface Preparations

PZT may be deposited on numerous substrates such as silica wafers, mica, fused quartz, borosilicate glass, Corning 7509 glass coated with stannic oxide based transparent conducting coating, and stainless steel, gold or platinum plates. Crack free surface coatings are most easily applied to conducting glass substrates but in the case of fused quartz it is preferable to first apply a special surface treatment as described in more detail below. Substrates must be thoroughly cleaned before depositing the coating, preferably by boiling in water with a detergent, rinsing in distilled water followed by ultra sound to remove organic contaminants and vapour degreasing in methanol. After cleaning, the precursor films, such as those described in Table 1, can be deposited on the substrate by spin coating, dip coating or by painting. The spin coating technique is preferred for flat substrate surfaces as the thickness of the film may be controlled by the speed of rotation of the spinner and the concentration and viscosity of the solution. A spinner such as a “Headway Research Incorporated photoresist spinner” operated at 8500 rpm for 20 seconds is particularly suitable. More complex shapes cannot readily be prepared by spin coating and recourse may be had to dip coating or painting. In this case it is usually necessary to dilute the above stock solution with propanol or a mixture of propanol and water. The film thickness can be controlled by the amount of propanol and water or the ratio of propanol to water and by controlling the speed of pulling the dip coated article.

Firing

Heretofore films made by sol gel processing have usually suffered macro cracking during firing. Such cracking can be substantially reduced or eliminated by the use of firing additives to the stock solution or, in certain cases, by deposition of an intermediate buffer layer.

After an organo-metallic film has been deposited and dried it must be pyrolysed to remove the organics and induce the solid state reaction which produces the PZT. An increase in the density of the film and sufficient time for a solid state diffusion reaction to take place are both required. The normal approach to avoid cracking is to pyrolyse the film rapidly by transferring the substrate to a surface which is well above the pyrolysing temperature. According to the present invention, the pyrolysis may be better controlled if the time or temperature range over which the film is in a viscous liquid state is extended. This may be accomplished by adding a relatively small amount of a firing additive selected from ethylene glycol, glycerol and tetra ethylene glycol to the stock solution in order to raise the viscous state temperature. The resulting films are crack-free, very transparent and have improved surface smoothness. Glycerol and tetra ethylene glycol are preferred additives. When using glycerol the wet film may be fired by raising the temperature gradually which is particularly advantageous especially when coating metallic substrates such as stainless steel or alumel.

It is known that in normal ceramics, firing cracks can be controlled if the material is maintained under a compressive load. In a preferred, and alternate, embodiment of the present invention, this technique may be applied and is particularly useful on substrates such as silicon and borosilicate glass. A thin intermediate or buffer layer may be deposited onto the substrate and fired on prior to the deposition of PZT. The thickness of the buffer layer depends on the substrate and film composition but 100 Å is usually sufficient. For applications requiring a transparent insulating layer Alumina (Al₂O₃) has good properties and is easy to fabricate by sol gel processing. A typical mixture f or this purpose is shown in Table 1 (b), above. For transparent, conducting coatings indium tin oxide or stannic oxide conducting coatings may be used. Other conducting coatings include Al, Au, Cr, Ni and Co which may be produced by known vacuum deposition or chemical techniques.

The firing schedule which pyrolyses the organo-metallic compounds to an inorganic film is key to the preparation of crack free films having the desired crystal structure, grain size, transparency and surface roughness. The solvents evaporate with a consequent large change in volume and the generation of internal stress at temperatures between room temperature and about 250° C. As the temperature increases the lead acetate dehydrates, melts and decomposes. At this stage, the dried film becomes “wet” again and the organic compounds begin to decompose. The internal stress is relaxed and the volume change of the film continues. At the end of this stage, the organic film changes to a fine mixture of oxides of lead, titanium, zirconium and free carbon. At still higher temperature, the free carbon oxidizes and the mixture of oxides transforms to a transparent amorphous PZT film.

It is believed that the high boiling point and latent heat of vaporization of the ethylene glycol raises the solution evaporation temperature in the first phase towards the “melt” temperature in the second phase. This retains atom mobility and significantly reduces the tendency to crack. Raising the firing temperature also reduces this tendency. Films can be fired either in an oven or by placing the substrate on a hot plate. In the latter case, the rapid rise in temperature and the fact that the substrate temperature is higher than the film temperature lead to fewer cracks in the fired film. As the wet film pyrolyses and solidifies on the hot expanded substrate, the tendency on cooling is to create compressive or lower tensile stress. There are, however, some limitations on the speed and temperature of firing. In the case of thick films, the firing temperature should be limited to 350° C.-550° C. as the films become milky and less transparent at higher firing temperatures.

Annealing

As fired films are basically amorphous and need annealing at temperatures up to about 600° C. for up to six hours in order to cause the amorphous structure to change to a perovskite structure.

Electrical Post Treatment

After annealing the crystal structure of the film is generally that of randomly oriented crystallites, although some evidence of at least some orientation exists. In order to induce piezoelectric properties, however, it is necessary to electrically pole the films by application of an electric field of between 2 and 3 KV/mm when the films are held at a temperature of about 175° C. Films produced by the aforesaid processing steps have been shown to have properties superior to those obtainable by other processing methods. For example, the best piezoelectric coupling coefficient heretofore achieved, in zinc oxide, is of the order of 0.7%. In contrast films according to the present invention have a piezoelectric coupling coefficient of at least 1.0%.

PZT thin films have numerous applications including use in electro-optic displays and electroluminescent devices. They are used in electronic applications such as ferro-electric gate insulators or capacitors in non-volatile memories. A third field of use includes high frequency ultrasonic transducers for non-destructive evaluation and medical and biological purposes, while a fourth field includes fibre optic sensors and devices.

While this invention has been described with particular reference to PZT and PLZT, it will be appreciated that the processing techniques described are equally applicable to the deposition of other complex oxide crack-free thin films such as those listed hereinabove. It has been found that the thickness of the crack-free film and the smoothness of the film can be controlled specifically by the composition and viscosity of the firing additive. Modification of the polyethylene glycol mixture is therefore important. It has also been found advantageous to process and fire under vacuum in order to extract the water uniformly and cause uniform decarbonization. 

1. A method of casting a refractory article comprising: providing a mold formed from a slurry composition comprising plaster and fibers, wherein the slurry composition comprises at least about 20% fibers by weight; adding a refractory composition to the mold; and allowing the refractory composition to set, wherein the refractory composition comprises colloidal silica.
 2. The method of claim 1 wherein the fibers comprise paper fibers.
 3. The method of claim 2 wherein the slurry composition comprises at least about 25% paper fiber by weight.
 4. The method of claim 1 wherein the density of the mold is less than about 60 lb/ft³.
 5. The method of claim 1 further comprising the step of providing a model of a refractory article and forming the mold thereof.
 6. The method of claim 5 further comprising the step of forming the mold from the slurry composition comprising plaster.
 7. The method of claim 6 wherein the slurry composition comprises plaster and paper fiber.
 8. The method of claim 1 wherein the refractory composition comprises at least about 55% alumina by weight.
 9. The method of claim I wherein the refractory composition comprises at least about 2% silicon carbide by weight.
 10. The method of claim 1 wherein the refractory composition comprises up to about 2% free carbon by weight.
 11. The method of claim 1 wherein the refractory composition comprises about 55% to about 90% alumina bV weight, about 2% to about 30% silicon carbide by weight, and about 2% to about 20% silica by weight.
 12. The method of claim 1 wherein the refractory composition comprises at least about 70% alumina by weight, up to about 20% silicon carbide by weight, and at least about 2% silica by weight.
 13. The method of claim 1 further comprising the step of heating the mold and the refractory composition.
 14. The method of claim 13 wherein the mold and refractory composition are heated at a temperature of at least about 800° F.
 15. The method of claim 13 wherein the mold and refractory composition are heated at a temperature of at least about 1000° F.
 16. The method of claim 1 wherein the refractory article is chosen from crucibles, kiln furniture, launder blocks, lentel blocks, nozzles, pouring cups, pouring tubes, pump tubes, shrouds, stopper rods, and tundishes.
 17. A refractory article made from the method of claim
 1. 18. A method of casting a refractory article comprising: providing a mold; adding a refractory composition to the mold; and heating the refractory composition, wherein the mold is formed from a slurry composition comprising plaster and at least about 20% fibers by weight, and wherein the refractory composition comprises about 55% to about 90% alumina by weight, up to about 30% silicon carbide by weight, and about 2% to about 20% silica by weight.
 19. The method of claim 18 wherein the fibers are paper fibers.
 20. The method of claim 19 wherein the slurry composition comprises at least about 25% paper fiber by weight.
 21. The method of claim 18 wherein the refractory composition comprises colloidal silica.
 22. The method of claim 18 wherein the refractory composition comprises about 70% to about 80% alumina by weight, about 10% to about 20% silicon carbide by weight, and about 5% to about 10% silica by weight.
 23. The method of claim 18 wherein the refractory composition comprises up to about 2% free carbon by weight.
 24. The method of claim 18 wherein the refractory composition is heated at a temperature of at least about 1000° F.
 25. The method of claim 18 wherein the refractory article is selected from crucibles, kiln furniture, launder blocks, lentel blocks, nozzles, pouring cups, pouring tubes, pump tubes, shrouds, stopper rods, and tundishes.
 26. A method of casting a refractory article comprising: providing a pattern of a refractory article; providing a slurry composition comprising plaster and at least about 20% fibers by weight; disposing the slurry composition around the pattern; allowing the slurry composition to set to form a mold; adding a refractory composition comprising colloidal silica to the mold; and heating the refractory composition.
 27. The method of claim 26 wherein the mold and refractory composition are heated at a temperature of at least about 1000° F.
 28. (canceled)
 29. The method of claim 26 wherein the refractory composition comprises about 55% to about 90% alumina by weight, up to about 30% silicon carbide by weight, and about 2% to about 20% silica.
 30. The method of claim 26 wherein the fibers are paper fibers.
 31. The method of claim 30 wherein the slurry composition comprises at least about 25% paper fiber by weight.
 32. The method of claim 26 wherein the refractory article is selected from crucibles, kiln furniture, launder blocks, lentel blocks, nozzles, pouring cups, pouring tubes, pump tubes, shrouds, stopper rods, and tundishes.
 33. A method of casting a refractory article comprising: providing a pattern of a refractory article; providing a slurry composition comprising plaster; disposing the slurry composition around the pattern; allowing the slurry composition to set to form a compliant mold with a density of between about 50 lb/ft³ and about 70 lb/ft³; adding a refractory composition comprising colloidal silica to the mold; and heating the refractory composition, wherein the mold degrades upon heating.
 34. The method of claim 1 wherein the density of the mold is between about 50 lb/ft³ and about 70 lb/ft³.
 35. The method of claim 18 wherein the density of the mold is between about 50 lb/ft³ and about 70 lb/ft³. 